Soil sampling and analysis for volatile organic compounds

Concerns over data quality have raised many questions related to sampling soils for volatile organic compounds (VOCs). This paper was prepared in response to some of these questions and concerns expressed by Remedial Project Managers (RPMs) and On-Scene Coordinators (OSCs). The following questions are frequently asked:

1. Is there a specific device suggested for sampling soils for VOCs?
2. Are there significant losses of VOCs when transferring a soil sample from a sampling device (e.g., split spoon) into the sample container?
3. What is the best method for getting the sample from the split spoon (or other device) into the sample container?
4. Are there smaller devices such as subcore samplers available for collecting aliquots from the larger core and efficiently transferring the sample into the sample container?
5. Are certain containers better than others for shipping and storing soil samples for VOC analysis?
6. Are there any reliable preservation procedures for reducing VOC losses from soil samples and for extending holding times?

Guidance is provided for selecting the most effective sampling device for collecting samples from soil matrices. The techniques for sample collection, sample handling, containerizing, shipment, and storage described in this paper reduce VOC losses and generally provide more representative samples for volatile organic analyses (VOA) than techniques in current use. For a discussion on the proper use of sampling equipment the reader should refer to other sources (Acker, 1974; U.S. EPA, 1983; U.S. EPA, 1986a). Soil, as referred to in this report, encompasses the mass (surface and subsurface) of unconsolidated mantle of weathered rock and loose material lying above solid rock. Further, a distinction must be made as to what fraction of the unconsolidated material is soil and what fraction is not. The soil component here is defined as all mineral and naturally occurring organic material that is 2 mm or less in size. This is the size normally used to differentiate between soils (consisting of sands, silts, and clays) and gravels. Although numerous sampling situations may be encountered, this paper focuses on three broad categories of sites that might be sampled for VOCs:

1. Open test pit or trench.
2. Surface soils (<5 ft in depth).
3. Subsurface soils (>5 ft in depth).

     

Naphthalene and its biomarkers as measures of occupational exposure to polycyclic aromatic hydrocarbons

Polycyclic aromatic hydrocarbons (PAH) include compounds with two or more fused benzene rings, many of which are carcinogens. Industrial sources produce hundreds of PAH, notably in the coke- and aluminium-producing industries. Because PAH are distributed at varying levels between gaseous and particulate phases, exposure assessment has been problematic. Here, we recommend that occupational exposures to naphthalene be considered as a potential surrogate for occupational PAH exposure for three reasons. Naphthalene is usually the most abundant PAH in a given workplace; naphthalene is present almost entirely in the gaseous phase and is, therefore, easily measured; and naphthalene offers several useful biomarkers, including the urinary metabolites 1- and 2-hydroxynaphthalene. These biomarkers can be used to evaluate total-body exposure to PAH, in much the same way that 1-hydroxypyrene has been applied. Using data from published sources, we show that log-transformed airborne levels of naphthalene are highly correlated with those of total PAH (minus naphthalene) in several industries (creosote impregnation: Pearson r= 0.815, coke production: r= 0.917, iron foundry: r= 0.854, aluminium production: r= 0.933). Furthermore, the slopes of the log-log regressions are close to one indicating that naphthalene levels are proportional to those of total PAH in those industries. We also demonstrate that log-transformed urinary levels of the hydroxynaphthalenes are highly correlated with those of 1-hydroxypyrene among coke oven workers and controls (r= 0.857 and 0.876), again with slopes of log-log regressions close to one. These results support the conjecture that naphthalene is a useful metric for occupational PAH exposure. Since naphthalene has also been shown to be a respiratory carcinogen in several animal studies, it is also argued that naphthalene exposures should be monitored per se in industries with high levels of PAH.     

EPA's monitoring program at Love Canal 1980

Summary As stated at the beginning of this paper conclusions reached thus far cannot be discussed in this paper. However, a great deal of information is available for examination.EPA displayed its ability to coordinate widely separated laboratories, both Federal and private, into a smooth working team in a very short period of time. A very comprehensive study plan was also developed and implemented quickly. EPA was fortunate to have already had GCA under contract when the emergency arose. In no small part the success of the field effort was due to the managerial and technical abilities of the GCA team.Within a period of 6 weeks a plan was developed, a prime contractor retained, subcontractors hired, and field activities begun. Within a period of 3 months in excess of 8600 field samples were collected and over 12,000 field and QC samples were analyzed. During this same period 2 major data systems were developed, debugged, and placed into operation.In short this EPA project was probably the most comprehensive multimedia field project ever attempted by EPA and certainly the data is being subjected to the most strenuous quality control measures ever imposed by this Agency. The entire program is presently under peer review and the results are being prepared for publication by EPA Headquarters.Note. Originally intended to be published as part of the special issue on Exposure Monitoring: An International Workshop (Las Vegas, Nevada, October 19–22, 1981).     

Dose-time-response functions for toxic chemicals

In many situations, the effect of a toxic chemical on a biological system depends on both the intensity and the duration of exposure. The dependence on the time dimension can be the expression of a range of processes including the physical accumulation of toxic chemicals or their metabolites and the functional accumulation of damage. Measures and functions that have been used to describe this dependence are reviewed.Some of these functions are compared through a case study of the neurotoxicity of methylmercury. Use is made of data that indicates a dependency between the blood concentration at which monkeys were exposed and the length of time before damage was detected. Several exposure functions are fitted to these data and their appropriateness is compared. Using the most appropriate function, an exposure-response relationship is developed using probit analysis. An alternative data analysis procedure is also investigated. The apparent threshold after a 100 day exposure is estimated to be greater by a factor of 3–5 compared to the threshold for chronic exposure. Applying this factor to man, the blood concentration threshold for chronic exposure is estimated to be 40–170 ppb, a finding consistent with recent reports of neurological damage in humans exposed below the generally accepted threshold.     

Problems of correlation of global and local monitoring of air pollution

1. The Air Polluttion Monitoring System has got a significant development of late, which is in direct relation with a considerable extention and improvement of the observation network in cities and industrial areas, with creation of a new network for assessing regional and global background of the atmosphere pollution, as well as with the wide involvement of meteorologists to monitoring organization.
2. While developing a new global monitoring system, it is necessary to take into account its relationship with the local monitoring within the region of air pollution sources, i.e. at the \lsimpact\rs level. The need in such an account is dictated first of all by the physics of pollutant spreading that states: changes in air pollution over large territories must be in a certain agreement with greater changes in the vicinity of emission sources. Methods applied in the global and local monitoring have also a number of common peculiarities. White organizing regional network for observations of the background pollution of the atmosphere twin stations (one of the pair of stations located outside the city boundaries in a small community, and the other, in the nearest city with the population of 200–400 thousand inhabitants) were established in the U.S.S.R. and in a number of socialist countries in Europe.
3. Implementation of the twin-station principles in the U.S.S.R. has contributed to data interpretation and representativity assessment as well as to correction of the station location. Observation results from the Soviet background stations and those abroad have been compared by now according to a number of indices.
4. The correlation of monitoring systems of various scales tells positively both on mutual improvement and completion of observational methods. The methods of obtaining integral characteristics of air pollution were used for the global monitoring, in particular spectral actinometric observations and chemical analysis of the precipitation composition. Now they find still wider employment. Thus methods of spectral actinometric measurements and data processing were used to estimate the degree of aerosol pollution of a number of industrial centres. The theory of solar radiation spreading and aerosol contents determination in urban atmosphere has also been developed. It is a generalization of an earlier developed theory, used to estimate global atmosphere pollution basing on actinometric data. The organization of precipitation collection and analysis on a network of stations around Leningrad and in Donbass area enables us to compare the admixture content in precipitations falling in industrial and agricultural areas.
5. A considerable increase of possibilities to measure microconcentrations of sulphur dioxide, nitrogen oxides and of a number of other pollutants is connected with the use of solid solvents for sampling. Their use will allow to avoid establishment of special laboratories at background stations and only send samples by post for their analysis in centralized laboratories.

They will also allow to considerably increase precision and accuracy of measurements. The international comparisons of methods of air pollution measurements on the background level allow to judge about the effiency of these methods.     

Indoor concentrations of carbon monoxide in selected urban microenvironments

CO concentrations were measured in five kindergartens, one children's hospital and two homes for aged, practically without indoor sources, all situated in the city centre, for ten random days in winter and ten in summer. The indoor CO concentrations were the result of the distance from and the traffic density in the nearest street, of general pollution level, seasonal differences, day-to-day variations and daily cycle of air pollution, the vicinity of traffic having a dominant influence. Therefore location of institutions for sensitive population groups in old city centres within a block of houses seems to be a suitable solution as far as exposure to CO is concerned.Revised version of a paper presented as poster at the VIth World Congress on Air Quality, Paris 1983.     

Determination of biomass burning emission factors: Methods and results

Biomass burning, in a broad sense, encompasses different burning practices, including open and confined burnings, and different types of vegetation. Emission factors of gaseous or particulate trace compounds are directly dependent both on the fuel type and the combustion process. Emission factors are generally calculated by stoichiometric considerations using the carbon mass balance method, applied either to combustion chamber experiments or to field experiments based on ground-level measurements or aircraft sampling in smoke plumes. There have been a number of experimental studies in the last 10 years to investigate wildfires in tropical, temperate, or boreal regions. This article presents an overview of measurement methods and experimental data on emission factors of reactive or radiatively active trace compounds, including trace gases and particles. It focuses on fires in tropical regions, that is, forest and savanna fires, agricultural burns, charcoal production, use of fuelwood, and charcoal combustion.     

Evaluation of the Industrial Source Complex short-term model in a large-scale multiple source region for different stability classes

The original Industrial Source Complex Model (ISCST, 90346) and its latest version, the ISCST2 (92090), are evaluated for the 1- and 24-hour averaging periods, using six statistical parameters. The confidence limits on two parameters were obtained using the bootstrap, jacknife, seductive, and robust resampling techniques. Evaluation is conducted in a multiple point source environment and in all the different stability categories, using a year of meteorological data, emission inventory of the Lucas County, in Toledo, Ohio, and monitoring data from two nearby stations for the year 1987. This was representative of a real time situation in which the ISCST is generally applied for regulatory work. The sensitivity analysis shows that the ISC is a poor performing model in the 1-h and 24-h averaging period, neutral and stable categories, and modifications to it are necessary in order to improve its performance. Its performance changes depending on the chosen paired values. A better relative performance is observed in the unstable category relative to the neutral and stable categories. Improved model performance may be achieved by applying modifications to the physics on which the model is based.